Iron-chromium-molybdenum oxide catalysts for methanol oxidation

The activity and selectivity of a precipitated iron-chromium-molybdenum oxide catalyst (Mo/(Fe + Cr) = 2.5/(0.5 + 0.5)) towards methanol mild oxidation have been studied by a flow-circulation method. Commensurable activity and selectivity with those of the industrial Fe₂ (MoO₄)₃-MoO₃ catalysts as well as an enhanced stability have been found. The Mössbauer spectra of fresh and tested catalysts show that during the catalytic reaction a partial reduction occurs and a steady state composition differing from the initial one is formed.     

The dynamic states of silica-supported metal oxide catalysts during methanol oxidation

The in situ Raman spectra of silica-supported metal oxide catalysts (containing surface metal oxide species of V, Nb, Cr, Mo, W and Re) were measured during methanol oxidation. Stable surface methoxy species were found to form via reaction with the surface Si---OH groups for all the catalysts investigated. The surface Si---OH groups were also titrated by the surface metal oxide species and the surface concentration of Si---OH groups decreases with increasing metal oxide loading. The stable surface M---OCH₃ were only found for the V₂O₅/SiO₂ catalysts. The surface metal oxide species were all influenced by the methanol oxidation reaction. The surface rhenium oxide species were removed from the silica surface and the surface molybdenum oxide species were partially agglomerated to crystalline β-MoO₃ particles by the formation of Re-methoxy and Mo-methoxy complexes. The surface niobium oxide and tungsten oxide species were partially reducing by the net reducing methanol oxidation environment. In situ Raman spectra for the CrO₃/SiO₂ catalysts could not be obtained due to the formation of reduced chromium oxide species during methanol oxidation which gave rise to sample fluorescence. The in situ Raman observations provided a fundamental basis for understanding the selectivity patterns of the silica-supported metal oxide catalysts during methanol oxidation. However, the mechanism by which the silica support ligands activate the redox properties of the surface metal oxide species is not completely understood.     

Complete oxidation of acetone over manganese oxide catalysts supported on alumina- and zirconia-pillared clays

The complete oxidation of acetone has been studied over a series of manganese oxide catalysts supported on the unpillared and the Al- and Zr-pillared forms of two natural clays of the smectite class (a montmorillonite and a saponite). The temperatures required for total combustion of acetone over the several catalysts ranged from 610 to 660 K at the relatively low W_Mn/F_in ratio of 0.40 g_Mn min mmol_acetone⁻¹ used. A significant influence of the clay supports characteristics on the catalytic performance has been found. According to the general behaviour of the various catalysts throughout the light-off tests, the following order of improving catalytic performance can be established with respect to the pillars composition: Al-pillared clays2O₃, MnO₂, Al₂O₃ and ZrO₂, as well as physical mixtures of ZrO₂ with the unpillared clays. The effect on the catalytic performance of the possible competition between the acetone combustion and aldol condensation processes has also been considered.     

Catalytic activity of copper and palladium based catalysts for toluene total oxidation

In this study, catalysts containing 0.5 wt.% of palladium or 5 wt.% of copper were compared towards toluene total oxidation using FAU Zeolite and ZrO₂ supports. A 0.5%Pd/NaFAU and 5%Cu/ZrO₂ were found to be promising catalysts for this reaction. Palladium presented then a better affinity for FAU zeolite and copper oxide had a better affinity for zirconia. The performances of Pd based catalysts were correlated to interaction between the active phase and the support whereas the activity of copper oxide was related to oxygen mobility property of the support leading to copper oxide particles easily reducible. Support modifications, yttrium addition for ZrO₂ and cation exchange for the zeolite FAU, still enhanced the catalytic activity. Therefore, 0.5%Pd/CsFAU and 5%Cu/Zr₉₅Y₅ samples were found to be interesting catalysts for total VOC oxidation.     

Total oxidation of ethanol and propane over Mn-Cu mixed oxide catalysts

Mn-Cu mixed oxides were prepared by co-precipitation varying the aging time for 4, 18 and 24 h. The catalytic performance in propane and ethanol total oxidation on these samples was better than on Mn₂O₃ and CuO pure oxides. The increase of the aging time enhanced the activity and the selectivity to CO₂. The nature and disposition of the phases forming the catalytic system as well as the effect of the precipitated aging time was determined by means of specific surface area measurements, X-ray diffractometry (XRD), infrared spectroscopy (FT-IR), X-ray photoelectron spectroscopy (XPS), temperature programmed reduction (TPR) and temperature programmed desorption of oxygen (O₂-TPD). The catalytic behaviour seems related to the existence of a Cu_1.5Mn_1.5O₄ mixed phase and the easier reducibility of the catalysts.     

Selective oxidation of methane to CO and H2 over unreduced NiO-rare earth oxide catalysts

NiO-LnO _x (Ln = lanthanide) catalysts (with NiLn=11) without prereduction show high activity/selectivity and very high productivity in the oxidative conversion of methane to CO and H₂. The catalysts are first activated in the initial reaction, which is started at 535–560°C, by the reduction of NiO and creation of active sites. The carbon deposition on the catalysts in the reaction, particularly for the NiO-Gd₂O₃, NiO-Tb₄O₇ and NiO-Dy₂O₃ catalysts, is quite fast but it has caused a little or no influence on the catalytic activity/selectivity. Pulse reaction of pure methane on NiO-Nd₂O₃ (at 600°C) shows involvement of lattice oxygen in the initial reaction and also reveals formation of carbon from CO on the catalyst reduced in the reaction.     

Partial oxidation of methane over silica supported molybdenum oxide catalysts

Two kinds of MoO₃/SiO₂ catalysts, MoO₃-I and MoO₃-S, were prepared by impregnation and sol-gel method, respectively. When MoO₃ loading was increased, formation of MoO₃ crystals was observed to begin at a MoO₃ loading of 8 and 16 wt% with MoO₃-I and MoO₃-S, respectively. The highest yield of formaldehyde from methane oxidation was attained also at those critical values of MoO₃ loading of 8 and 16 wt% over MoO₃-I and MoO₃-S, respectively. It is suggested that the active species for formaldehyde formation is well dispersed molybdenum oxide clusters on SiO₂ support: the optimum dispersion of the clusters affords the highest activity for formaldehyde formation.     

Evaluation and characterization of Mn-Cu mixed oxide catalysts supported on TiO2 and ZrO2 for ethanol total oxidation

MnCu/ZrO₂T and MnCu/TiO₂T (T = calcination temperature) catalysts were prepared by the sol-gel method with a Mn:Cu = 5:1 ratio and calcined at different temperatures, T = 673, 873 and 1073 K. The samples were characterized by X-ray diffraction, measurement of specific surface area, temperature programmed reduction, XPS and FT-IR spectroscopy. For both groups of catalysts, the increase of calcination temperature produced three effects: the segregation of phases, an increase of the crystallinity, and a phase transformation of the support. The catalytic activity was evaluated in total oxidation of ethanol, considered as model molecule of VOC. The MnCu/TiO₂ 673 and MnCu/ZrO₂ 873 catalysts showed the best catalytic performance, which was associated with the high dispersion of the MnO_x and CuO_x active phases. The catalytic activity of MnCu/TiO₂ 673 catalyst was also favored by its high surface area.     

Honeycomb supported perovskite catalysts for ammonia oxidation processes

Pechini route (M.P. Pechini. U.S. Patent no. 3,330,697 (1967)) was used for supporting perovskite – like systems LaBO₃ (B = Mn, Fe, Co, Ni, Cu) on thin-wall (0. 35 mm) cordierite honeycomb support with low thermal expansion coefficient to prepare stable to thermal shocks supported catalysts for high-temperature processes of ammonia oxidation into NO in nitric acid production. In this preparation route, perovskites (2–6%) have nearly uniform distribution in the walls as well as form surface grainy perovskite layer 2–3 μm thick that may be also important for the high temperature processes occurring at short contact times. Cordierite supported lanthanum manganite and cobaltite are the most active in the reaction of ammonia oxidation into NO especially when supported twice or on a secondary sublayer (Ln₂O₃, ZrO₂, MeO, LaBO₃).     

In situ IR,Raman, and UV-Vis DRS spectroscopy of supported vanadium oxide catalysts during methanol oxidation

The application of in situ Raman, IR, and UV-Vis DRS spectroscopies during steady-state methanol oxidation has demonstrated that the molecular structures of surface vanadium oxide species supported on metal oxides are very sensitive to the coordination and H-bonding effects of adsorbed methoxy surface species. Specifically, a decrease in the intensity of spectral bands associated with the fully oxidized surface (V⁵⁺) vanadia active phase occurred in all three studied spectroscopies during methanol oxidation. The terminal V = O (∼1030 cm⁻¹) and bridging V–O–V (∼900–940 cm⁻¹) vibrational bands also shifted toward lower frequency, while the in situ UV-Vis DRS spectra exhibited shifts in the surface V⁵⁺ LMCT band (>25,000 cm⁻¹) to higher edge energies. The magnitude of these distortions correlates with the concentration of adsorbed methoxy intermediates and is most severe at lower temperatures and higher methanol partial pressures, where the surface methoxy concentrations are greatest. Conversely, spectral changes caused by actual reductions in surface vanadia (V⁵⁺) species to reduced phases (V³⁺/V⁴⁺) would have been more severe at higher temperatures. Moreover, the catalyst (vanadia/silica) exhibiting the greatest shift in UV-Vis DRS edge energy did not exhibit any bands from reduced V³⁺/V⁴⁺ phases in the d–d transition region (10,000–30,000 cm⁻¹), even though d–d transitions were detected in vanadia/alumina and vanadia/zirconia catalysts. Therefore, V⁵⁺ spectral signals are generally not representative of the percent vanadia reduction during the methanol oxidation redox cycle, although estimates made from the high temperature, low methoxy surface coverage IR spectra suggest that the catalyst surfaces remain mostly oxidized during steady-state methanol oxidation (15–25% vanadia reduction). Finally, adsorbed surface methoxy intermediate species were easily detected with in situ IR spectroscopy during methanol oxidation in the C–H stretching region (2800–3000 cm⁻¹) for all studied catalysts, the vibrations occurring at different frequencies depending on the specific metal oxide upon which they chemisorb. However, methoxy bands were only found in a few cases using in situ Raman spectroscopy due to the sensitivity of the Raman scattering cross-sections to the specific substrate onto which the surface methoxy species are adsorbed. This revised version was published online in August 2006 with corrections to the Cover Date.     

Complete oxidation of benzene on Co---Cr and Co---Cr oxide catalysts

Supported mixture metal oxide systems, Cu---Cr and Co---Cr on γ-A1₂O₃ and γ-A1₂O₃+ SiO₂ were prepared and studied. They exhibited catalytic activity in the complete oxidation of benzene.     

Oxidative dimerisation of methane on supported palladium oxide catalysts

Supported palladium oxide catalysts are able to convert CH₄ to C₂H₆, CO, CO₂, H₂ and H₂O at temperatures 315 °C. Catalysts did not show any support effect when TiO₂, Al₂O₃, ZrO₂, La₂O₃ and MgO were used as supports. With sequential O₂ pulsing the catalyst showed long term activity when used at temperatures below 400 °C. Addition of Pt increased selectivity whereas with Ga it decreased. Results indicate participation of lattice O₂ from catalyst in the reaction pathway.     

Transient kinetics of toluene partial oxidation over V/Ti oxide catalysts

Transient kinetics in the toluene oxidation over V/Ti oxide catalysts prepared by grafting and impregnation have been compared. V⁴⁺ cations are supposed to be the sites for the formation of electrophilic oxygen species participating in deep oxidation. Another oxygen species (probably nucleophilic) present on the oxidised catalyst surface are responsible for benzaldehyde formation. Selectivity of 80–100% can be obtained during the initial period of the reaction on the grafted catalysts in the presence of gaseous oxygen and during the interaction of toluene (without O₂ in the mixture) with partially reduced catalysts.     

Ethanol oxidation on carbon supported platinum-rhodium bimetallic catalysts

Platinum is the most investigated catalyst for the electrochemical oxidation of small organic molecules. This metal presents high overpotentials for the oxidation of organic compounds and the poisoning of active sites by strongly adsorbed intermediates, mainly CO, which decrease the efficiency of a direct alcohol fuel cell (DAFC). Ethanol is an ideal fuel for these DAFC systems due to its high energy density, but one of the problems with the electro-oxidation of this fuel is the low yield for the total oxidation to CO₂. The purpose of the work reported here was to study the influence of the composition of Pt-Rh/C catalysts on the CO₂ yields. In addition, using the differential electrochemical mass spectrometry (DEMS) technique, it is shown that Pt-Rh/C catalysts enhance the total ethanol oxidation with respect to pure Pt/C by driving the reaction via the CO₂ route. The faradaic current efficiency for the oxidation of ethanol to CO₂ increased from 0.08 on pure Pt/C to 0.5 on the Pt₄₇Rh₅₃/C catalyst at 0.7 V vs. RHE. It was concluded that electronic effects play a key role in the mechanism of ethanol oxidation on Pt-Rh/C electrodes.     

Iron—molybdenum—oxide catalysts for selective oxidation of hydrogen sulfide to sulfur

The selective oxidation of hydrogen sulfide to sulfur was studied over iron-molybdenum oxides with various Fe-Mo ratios. Strong synergistic phenomenon in catalytic activity was observed for the Fe-Mo-O binary oxides. Under identical reaction conditions, the areal rates of the binary oxides were superior to those of the corresponding single oxide catalysts, which suggest that the new compound Fe₂(MO₄)₃ formed in the binary oxide is more active than Fe₂O₃ and MoO₃. The oxidation rates of H₂S were found to exhibit first-order dependence on the hydrogen sulfide concentration, which implies that the activation of H₂S is the rate-limiting step.     

Performance and characterization of supported metal catalysts for complete oxidation of formaldehyde at low temperatures

Activities of a series of metals (Pt, Pd, Rh, Cu, Mn) supported on TiO₂ were investigated for the catalytic oxidation of formaldehyde. Among them, Pt/TiO₂ was found to be the most promising catalyst. Nitrogen adsorption, hydrogen chemisorption, X-ray diffraction (XRD), transmission electron microscopy (TEM) and temperature programmed reduction (TPR) by H₂ were used to characterize the platinum catalysts. Using Ce_0.8Zr_0.2O₂, Ce_0.2Zr_0.8O₂, SiO₂ as supports instead of TiO₂, the activity sequence of 0.6 wt.% platinum with respect to the supports is TiO₂ > SiO₂ > Ce_0.8Zr_0.2O₂ > Ce_0.2Zr_0.8O₂, and this appears to be correlated with the dispersion of platinum on supports rather than the specific surface areas of the catalysts. Platinum loading on TiO₂ has a great effect on the catalytic activity, and 0.6 wt.% Pt/TiO₂ catalyst was observed to be the most active, which could be attributed to the well-dispersed platinum surface phase. The reduction temperature greatly affects the particle size and, consequently, the catalytic activity. The smaller particle size of platinum, due to its high dispersion on support, has a positive effect on catalytic performance. Increasing formaldehyde concentration and space velocity exhibits an inhibiting effect on the catalytic activity.     

Evaluation and characterization of Mn-Cu mixed oxide catalysts for ethanol total oxidation: Influence of copper content

Mixed oxides of manganese and copper with different wt% of copper have been prepared and evaluated in ethanol combustion. The co-precipitation method used for the synthesis of MnxCuy mixed oxides is adequate to obtain catalysts with excellent catalytic performance in combustion reactions. Catalysts were characterized by means of XRD, FT-IR, TPR and O₂-TPD. A small amount of copper prevents manganese oxide reaching a crystalline structure. This poor crystalline structure of manganese oxide may improve the existence of oxygen vacancies giving a best performance in ethanol combustion to CO₂. When the copper content increases, an extent of solid state reaction between Cu and Mn is favored and the partial oxidation of ethanol becomes more important. The incorporation of manganese into incomplete spinel structure diminishes CO₂ yield.     

Low-temperature mild partial oxidation of ethanol over supported platinum catalysts

Supported platinum catalysts containing 1.2% Pt loaded on Al₂O₃ (1.2% Pt/Al₂O₃) and 1.9% Pt loaded on ZrO₂ (1.9% Pt/ZrO₂) were prepared by incipient wetness impregnation and sol–gel method, respectively. The activity of these catalysts in the partial oxidation of ethanol (POE) was examined in a fixed-bed reactor in a temperature range between 373 and 473 K. The results indicated that significant ethanol conversion (C_EtOH > 50%) was found at the low reaction temperature with a feed ratio of O₂/EtOH ratio >0.75. Oxygen molecules introduced in reactant were completely consumed in POE reactions performed. H₂, H₂O, CO and CO₂ were the major products detected. The selectivity of hydrogen (S_H2) and CO (S_CO) varied significantly with reaction conditions. High selectivity of hydrogen (S_H2 > 95%) and low selectivity of CO (S_CO  0%) were found from a mild oxidation at T_R = 373 K over Pt/ZrO₂. However, these two selectivities were drastically deteriorated through oxidation at high T_R, high O₂/EtOH ratio or over Pt/Al₂O₃ catalyst.     

Complete oxidation of short chain alkanes using a nanocrystalline cobalt oxide catalyst

Exceptionally high activity for the complete oxidation of propane is reported for the first time using a nanocrystalline cobalt oxide catalyst. The catalyst shows stable activity for prolonged time on stream and when the reaction temperature is cycled. Furthermore, the nanocrystalline catalyst demonstrates considerably higher activity than an alumina supported palladium catalyst, which is recognised as one of the most active reported. The high activity of the cobalt oxide catalyst is associated with the nanocrystalline nature of the material, which gives rise to new catalytically active surface sites. A broader comparison with other reported high activity catalysts emphasises the high efficacy of nanocrystalline cobalt oxide for total oxidation and demonstrates that it has significant potential for important applications, such as control of emissions from liquid petroleum gas powered vehicles and alkane volatile organic emissions from stationary sources.     

Low temperature incineration of mixed wastes using bulk metal oxide catalysts

Volume reduction of low-level mixed wastes from former nuclear weapons facilities is a significant environmental problem. Processing of these materials presents unique scientific and engineering problems due to the presence of minute quantities of radionuclides which must be contained and concentrated for later safe disposal. Low-temperature catalytic incineration is one option that has been utilized at the Rocky Flats facility for this purpose.

This paper presents results of research regarding evaluation of bulk metal oxides as catalysts for low-temperature incineration of carbonaceous residues which are typical by-products of fluidized bed combustion of mixed wastes under oxygen-lean conditions. A series of 14 metal oxides were screened in a thermogravimetric analyzer, using on-line mass spectrometry for speciation of reaction product gases. Catalyst evaluation criteria focused on the thermal—redox activity of the metals using both carbon black and PVC char as surrogate waste materials. Results indicated that metal oxides which were P-type semiconductor materials were suitable as catalysts for this application. Oxides of cobalt, molybdenum, vanadium, and manganese were found to be particularly stable and active catalysts under conditions specific to this process (T < 650°C, low oxygen partial pressures).

Bench-scale evaluation of these metal oxides with respect to stability to chlorine (HCl) attack was carried out at 550°C using a TG/MS system. Cobalt oxide was found to be resistant to metal loss in a HCl/He gaseous environment while metal loss from Mo, Mn, and V-based catalysts was moderate to severe. XRD and SEM/EDX analysis of spent Co catalysts indicated the formation of non-stoichiometric cobalt chlorides. Regeneration of chlorinated cobalt was found to successfully restore the low-temperature combustion activity to that of the fresh metal oxide.